Derivatives of glycols



Patented Feb. 5, 1946 UNITED s1- -r s PATENT OFFICE v W 11223: otrcons I Robert P. Parker,

ton, Bound Brook, N. Cyanamid Company, ration of Maine Somerviile, and John J. non- J., assignors to American New York, N. Y., a corpo- No Drawing. Application July 3, 1944, Serial No. 543,421;

momma. .(cL'zco-s'ni This invention relates to new aminoaryl derivatives of 'glycols having from two to four carbon atoms. The compounds may be represented by the following formula:

in which G is the residue of a glycol having not less than two and not more than four carbon atoms and X is a paranitroor paraminophenyl radical. The modification of the invention in which X' is paraminophenyl is the more important one as those amino compounds are capable of diazotization and coupling with various coupling components, particularly ice-color coupling components which make possible new blue to violet pigments and dyes exhibiting superior fastness properties such as iastness to light, heat and washing.

The amino compounds of the present invention form salts with strong acids. When used as color. bases for azo dyestuffs, the salts give the same result 'as the free bases and, in fact, in many casesare more convenient to use. The present invention, therefore, includes both the bases and their salts particularly salts of common acids such as hydrochloric acids. p

The preferred bases of the present-invention having primary amino groups may also be transformed into stabilized diazo compounds such as, for example; diazo sulfonates and diazo salts.

procedures in the conventional manner.

It is an advantage of the present invention that I the process of producing the glycol derivatives of I caustic alkalies and it These products maybe used in various dyeing the present invention is not 'critical and can be carried outwith satisfactory yields;

In general, the best-results are obtainedby reacting 4'-hydroxy-4-nitro diphenylamine or its 2-sulfonic acid derivative with an ester of a glycol desired. The product obtained is a nitro product which can be reduced to the preferred amino products by conventional reduction processes using ether alkaline -or acidic reducing agents.

'organic acids may paratoluene sulfonic pylene glycol, l-methyl propylene glycol, l ethylethylene glycol, butylene glycols, diethylene glycol, thiodiglycol and the derived therefrom. The acidic radical of the estcr is not particularly critical thus for example:

alkylene dihalides which are the glycol esters of hydrohalic acids may be usedor glycol esters of be employed among which acid is very satisfactory. The first step of the reaction is preferably carried out in the presence of strong alkalies is an advantage that the process may be carried out in aqueous medium which avoids the problem of solvent recovery.

sulfoxide and suiione such as The invention will be illustrated inconiunction with the following examples which are typical. All parts are by weight unless otherwise noted.

. Ex mple 1 N,N'-bis(4"-nitrophenyl)-4,4'-aminophenyl ethylene glycol ether 34.8 parts of potassium 4'-hydroxy-4-nitrodiphenylamine-2-sulfonate, and 6.2 parts of potassium hydroxide are dissolved in 100 parts. of water, 18.5 parts of ethylene glycol di-p-toluenesulionate are added and the mixture is heated under gentle reflux for about 6 hours. After a short time, the solution becomes opaque and a solid starts separating; the solid continues to increase irfamount during refluxing. The reaction mixture is chilled, and the yellow solid is collected on a filter and dried. The crude dipotasslum salt of N,Nf-bis- (4"- nitro-2"-sulfophenyl) 4,4'-aminophenyl ethylene glycol ether is purified by being salted with potassium chloride from a hot aqueous solution.

A slurry of 36.1 parts or this dipotassium t in 428 parts concentrated hydrochloric acis is be of any of the glycols a heated under reflux for 19 hours. During. this time, the slurry changes. in color from a bright lemonyellow to an orange. After refluxing, the.

reaction mixture is poured into 1,000 partsof water, and the undissolved solid is collected on a filter. This; solid is washed free of acid on the filter with water, and is dried. .This crude product is extracted with acetone,-and N,N'-bis-(4 nitrophenyl) 4,4 aminophenyl ethylene glycol ether is reprecipitated from the acetone by addition of water. when further purified by recrys tallization from dilute dioxane, it melts at 184- scribed in Example 1 are stirred into 136 parts of solid which forms is collected on a filter and is ethylene glycol ether dihydrochloride crystallizes out. It is N ,N'-bis-(4"-nitrophenyl)-4,4'-aminophenyl propylene glycol ether ether is obtained Example 2 N.N'-bis- (4"aminophenyl) -4,4'-aminophenyl ethylene l ether 8 7 CHr-OONHONHi-HCI LEs-OONHONmHCi 12 parts of -,N,N':bis-(4"nitrophenyl)-4.4'-aniinophenyl ethylene glycol ether prepared as dem not of Example 1: N.N'-bis-(4"-aminophenyl)- 4,4'-aminophenyl proplene glycol ether is obtainedinpure to i Example 5 A slurry of 5 parts of N,N'-bis-(4"-aminophenyl) -4,4'-aminophenyl ethylene glycol ether dihydrochloride as obtained in Example 2 in 40 parts of water and 20 parts of 17% hydrochloric acid is stirred at 40 C. while a solution of 1.6

parts of sodium nitrite in 23 parts of water is slowly added. After stirring for minutes, 10

glacial acetic acid and heated to 70 C. A solu: tion of 44.5 parts ofstannous chloride dihydrate in 149 parts of concentrated hydrochloric acid is J gradually added over a period of time. The reduction is allowed to proceed at a temperature of 70-80 C. for 3 hours at which time the solu-- tion is cooled and is treated with sodaash until it is no longer acidic to Congo red paper. It is then made strongly basic to phenolphthalein with sodium hydroxide solution. The white cipitate is filtered oil. The residue is reslurried in 80 parts of fresh water, is made acidic to Congo red test paper with dilute hydrochloric acid, charcoal is added and the temperature is raised to C. The resulting solution is filtered and thefiltrate' is chilled. On additon of 8 parts of salt, a golden yellow solid precipitates which is filtered oil and is dried at low temperature. 'The tetrazonium chloride of I N,N'-bis-(4"-aminophenyl) -4,4' -aminophenyl ethylene glycol ether is a yellow solid, soluble in water. I

5.4 parts'of the dry tetrazonium chloride as obtained above are well mixed with 4.9 parts of then reslurried in 500 parts of water kept strongly alkaline to phenolphthalein with sodium hydroxide. This solid is reoollected on a filter, jand is washed with water until free of alkali. It is then slurried in approximately 400 parts of water and hydrochloric acid is added until the slurry magnesium sulfate dihydrate and 2.5 parts of anis acidic to Congo red test paper 0n heating, hydmus sodium sulfatethe solid dissolves, charcoal is added, and the 02 part f h mixture slurfled in Parts solution is filtered. On chilling, the filtrate, f methanol is .trfiated with Parts Of the N,N'-b1s-'(4"-aminopheny1) 4 4 auilide of 2-hydroxy-3-naphthoic acid in 2.5

parts of methanol and 5 parts of pyridine whereupon ablue-black paste results. This is heated 10 minutes on a steam bath, is diluted with 200 amlnophenyl collected on a filter d ccator It is purified by from dilute hydrochloric acid.

7 Example 3 and dried in a recrystallization phthale'in paper is obtained. The precipitated dyestufi is fiocculated by digestion on a steam bath, is filtered oh, the residue being' washed with hot water, thenwith dilute hydrochloric acid and finally with hot water.

After drying, a blue-black, water-insoluble pigment is obtained CHpGB-OGNHONO; V

lHr-OONHONOi liq-NONHOOCHiOH|0-ONHONN 1 on 05 I CW0 l G the procedure of Example 1 was followed except I 19.; parts of propylene glycol di-p-toluenesulwhen in the above preparation, an equivalent fonate was used instead of 18.5 parts of ethylene weight of beta naphthol is substituted, for the glycol 'di-p-toluenesuli'onate. The N,N'-bis-(4"- anilide of z-hydroxy-s-naphthoic acid,fa deep nitrophenyl)-4,4'-aminophenyl propylene glycol -blue-black, water-insoluble pigment is formed as an orange-yellow solid. which has the following formula:

on a V Example 6 N,N -bis-(y aminop e yD-gd amlnophenylpmpyleneglyooieghor A p inting paste is prepared by. dissolving 2 Nmnc, parts of the blended mixture or the tetrazonium CH OH-O O v chloride as made in Example 5 in 25 parts of l I l v water and'adding thereto '73 parts of a suitable m-oONnONmnci carbohydrate thickener. the procedure of Example 2 was followedsub- 'E'zample 4 i (lotion piece goods are wetted in a warm which has the following forstituting the product 01' Example 3 for the, prodparts of sodium chloride are added and the presoap solution, are rinsed, passed between squeeze the remaining portion an alkaline clearing bath /2% soap solution, finally 2-hydroxy-B-napbthoic acid (f-naphthylamide) acid (2- z-hydroxg'carbazole-li-earboxylic acid (2-met rolls and impregnated with the coupling component by passing through a warm solution of 5.0 parts of the anilide of 2-hydroxy-3-naphthoic acid, parts of methanol, 20 parts of 20% sodium hydroxide, and 4'70 parts of water. After passing between squeeze rolls, the fabric is dried.

A part of the above prepared print pasteis printed from an engraved copper roll upon this prepared cloth. The print is 'skyed and is dried at 65 C. It is then cleared at 70 C. in an alkaline bath (3% soda ash and 2% sodium hydroxide), is treated at 65 C. in a s'oap solution, rinsed and dried.

The pattern is printed a bright blue of greenish The substitution of the'beta-naphthylamide or 2-hydroxy-3-naphthoic acid for the anilide in the above alkaline grounding liquor produces animpregnated fabric which when printed upon by oi the printing paste and when finished by a similar procedure produces considerably deeper shade of blue.

Example 7 Cotton piece goods are separately impregnated with ice-coupling components by the procedure described in Example 6.

5 parts of the cotton piece goods so prepared are dyed in separate bufiered tetrazo baths oi the above compositionuntil color development is The dyeings are treated at 90 C. in (3% soda ash and 2% sodium hydroxide), then treated at 65 C. in a rinsed and dried. Some of the colors produced according to the articular ice-color coupling component taken in complete.

the alkaline grounding bath are listed below:-

Ice-color coupling component 7 Color z hydroxy-a-naphthoic an anilide Stro .blue. z-hydroxy-a-naphthoic. acid (iY-methyl anilide)... Red 11 blue. Bis-(acetoacetie)-o-tolidide Yellow-brown.

Bluish green.

Reddish blue. Brown.

z-hydrox -anthracene-3-carboxylic methy anillde). j

z-hydroxy-a-naphthoic acid (iY-ethoxy anilidez .1.

anilid amine-2-sultonic acid in which G is the atoms and X represents a'para aminophenylradical. a

2. An ethylene glycol derivative having the following formula:

NHX

, in which X represents a para aminophenyl radical.

3. A glycol derivative having the followin formula:

in which and not more than four carbon atoms.

4. An ethylene glycol derivative having the following formula: 7

- CHr-O-O-NH-O-NH:

A salt of a compound of claim 1. A salt of a compound of claim 2. A salt or a compound of claim 3.

8. A salt of a compound of claim 4.

9. In a process of preparing glycol ethers of 4'-hydroxy-4-nitro diphenylamine the step which comprises reacting 4'-hydroxy-4-nitro diphenylwith an ester of a glycol containing not less than two and not more than four carbon atoms in the presence of a strong alkali.

- 10. In a process of preparing ethylene glycol ethers of 4'-hydroxy-4-nitro diphenirlamine the step which comprises reacting 4'-hydroxy-4-nitro diphenylamine-2-sulionic acid with an ester or ROBERT P. PARKER. JOHN J. BENTON.

We claim: a 1. A glycol derivative having the following- G is a glycol having not less than two 

